high performance stabilizer with enhanced hydrolytic

Confidential

Dr. Hartmut Siebert, MSc

BU Additives

BL Performance Additives

17.01.2019

High performance stabilizer with enhanced hydrolytic stability and reduced NIAS

Dr. Hartmut Siebert, MSc, BU Additives, BL Performance Additives, 17.01.2019

Table of Contents

Confidential, High performance stabilizer with enhanced hydrolytic stability and reduced NIAS2

– Clariant History

– AddWorks Solutions

– Benefits for extrusion process

– Evaluation of hydrolytic stability

– Adding Value to High Speed BOPP

– Cost efficient solution for LLDPE processing

– Long Term Heat Stabilization

– Product Form

– Key Benefits


Clariant History

Public, Performance, Growth and Innovation3

1995 2000 2006 2011 2012 2015 2017 2018

1995

Clariant Swiss parent

company created in a

spin-off and subsequent

IPO of the Sandoz

Chemicals Division

1997

Acquisition of Hoechst AG

specialty chemicals

business

2000

Acquisition of British BTP

2001 – 2007

Divestment of several

bigger businesses due to

financial difficulties resulting

from BTP acquisition

2006

Acquisition of Ciba

Masterbatches

Divestment of

Pharmaceutical Fine

Chemicals

2008

Change in management

2009

Launch of Clariant

Excellence

2009 – 2010

Restructuring phase

2011

Acquisition of Süd-Chemie

Roll-out of new Clariant

Corporate Values

2012

Clariant rebranding

Introduction of new

corporate mission and

vision

2013

Opening Clariant

Innovation Center in

Frankfurt, Germany

2013 – 2014

Divestment of 5

businesses

2014

Sustainability

becomes strategic pillar

2015

Establishment of Global

Business Services

Clariant celebrates its 20th

birthday

2016

Acquisition of Kel-Tech

and X-Chem in the U.S.

2017

Announcement of planned

merger with Huntsman

White Tale Holdings steps

in

Termination of merger

Strategy update started

2018

SABIC becomes Clariant’s

biggest shareholder by

acquiring the stake of White

Tale

Clariant and SABIC sign

memorandum of

understanding and

governance agreement


AddWorks Solutions


– A unique combination of a differentiated

chemical formulation offered in the most-

convenient-to-handle physical form.

– Solutions developed by Clariant Polymer

Additives to satisfy specific market needs.

– By leveraging on Clariant`s products,

expertise, know-how, production

capabilities, AddWorks remove complexity

and cost at our customers.


Fully integrated approach to provide customer specific performance


Customer specific benefits in a fully integrated way.

Low migration

Enhanced metallisation

In-process cleaning

Cost efficiency

Superior colour

Enhanced melt stability

Excellent hydrolytic stability

Low gel formation

Low water carry over

Enhanced pressure pipe life-time

AddWorks LXR 5 solutions

Benefits for extrusion process


Melt formation and extrusion


Several critical zones for polymers in the extrusion process

shearO2

hopper with polymer

drive

melt formation zone hot barrel filling channel

screen packcompression zoneheating jacket

high flow

velocity

heat

die


Addworks LXR 568 is activated early during plastic processing and efficiently protecting the resin melt


The low melting temperature of AddWorks LXR 568 contributes to a superior melt homogeneity and

an efficient reduction of gels and defects in films.

Softening temperature interval

AddWorks LXR 568

Typical melting point of

single stabilizer

i.e. Phosphite 168 or

Cyclic Phosphite 626

ca. 90 °C

See the

difference

ca.180 °C_

_

_

_

_

_

_

_

_

_

Evaluation of hydrolytic stability


Hydrolysis Stability in PE Zip Bag

DTBP CONTENT (%)


Significant higher hydrolytic stability vs specialty phosphites. Easy to handle.

Formation of NIAS is retarded.

PS 168

PS 626

PS 627

P-EPQ

LXR 568

MONTH

0

5

10

15

20

25

30

35

40

0 2 4 6 8 10 12 14


Processing StabilizerExperiment – Hydrolytic stability test


Stored in oven set at 60 C

Figure: Hopper car testing system

The Hopper car test generates a saturated humidity atmosphere


Hydrolysis stability in Hopper Car Test


0

10

20

30

40

50

60

70

80

90

0 500 1000 1500 2000

DTB

P (%

)

Hour

Hostanox P-EPQ

AddWorks LXR 568

PS 626

PS 627

PS 168

– Significant higher hydrolytic stability vs specialty phosphites. Easy to handle.

– Formation of DTBP is deferred.

Confidential

Dr. Hartmut Siebert, MSc

BU Additives

BL Performance Additives

17.01.2019

Evaluate comparative cleaning effect of HostanoxP-EPQ versus LXR 568 in LLDPE


Appearance of initial screw


Blank initial screw


Appearance of screw after MB production and after keep it under room temperature for 1 day


Immediate after MB production After keep for 1 day

After production of LLDPE Masterbatch with 10% P-EPQ screw gets rusty


Appearance of screw after MB production and after keep it under room temperature for 1 day


Immediate after MB production After keep for 1 day

After production of LLDPE Masterbatch with 10% AddWorks LXR 568, screw looks nice and clean


Number of gels in LLDPE films with MB - Compounding process with rusty screw


0

20

40

60

80

100

120

140

LLDPE 1000 ppm LXR 568 1000 ppm P-EPQ

De

fec

t (1

/m2

)

Film thickness: 30 µm, Measurement area: 3 m2, Camera FSA 100 of OCS, Dark level: -50-25%

50-100 µm100-200 µm200-300 µm300-400 µm400-500 µm>500 µm

Note: Rusty screw and barrel was used to compound the formulations after purging screw by commercial LLDPE

Less gels with AddWorks LXR 568 compared to P-EPQ


Number of total gels in LLDPE films with MB - Compounding process with rusty screw


145.63

98.52

149.27

0

20

40

60

80

100

120

140

160

LLDPE 1000 ppm LXR 568 1000 ppm P-EPQ

De

fec

t (1

/m2

)

Film thickness: 30 µm, Measurement area: 3 m2, Camera FSA 100 of OCS, Dark level: -50-25%

Note: Rusty screw and barrel was used to compound the formulations after purging screw by commercial LLDPE

34 % less gels with AddWorks LXR 568 compared to P-EPQ

Adding Value toHigh Speed BOPP


High Processing stability for BOPP film grade


Additive loading can be reduced by a factor of 2 to 3

Less plate out, less blooming, less die built-up

44 % better MFR protection than PS 168

68 % better color protection than PS 168

No color improvement by increasing concentration of PS 168

MFR 230 °C / 2.16 KG (G/10MN) YELLOWNESS INDEX

Base Resin: BOPP, MFR = 2.0; Base Stabilization: 300 ppm Hycite 713 + 500 ppm AO 1010

Pass 0 Pass 1 Pass 3 Pass 5

2

3

4

5

6

7

8

0.07 % PS 168 0.1 % PS 168 0.14 % PS 168 0.07 % LXR 568

Pass 0 Pass 1 Pass 3 Pass 5

-202468

101214

0.07 % PS 168 0.1 % PS 168 0.14 % PS 168 0.07 % LXR 568

BAD GOOD BAD GOOD

Cost efficient solution for LLDPE processing


General requirements for film


– Melt and color stability

– High transparency

– Low gels

– Even film thickness profile


Processing of LLDPE (0,918 g/cm³) at 240°C

MELT FLOW INDEX (MFI, 190°C/2,16 KG) [G/10MIN]


Superior MFR retention of LLDPE stabilized with solutions based on AddWorks LXR 568

0.2

0.5

0.8

1.1

1 2 3 4 5

0.15% AddWorks LRX 568

Base stabilization:

0,1% AO 1076 +

0,1% Ca-stearate


0.20% PS 168

EXTRUSION PASSES (30 SEC/PASS RESIDENCE TIME)

Without Proc. Stab.


Processing of LLDPE (0,918 g/cm³) at 240°C

YELLOWNESS INDEX (PELLETS)


Outstanding YI protection for LLDPE stabilized with solutions based on AddWorks LXR 568

YELLOWNESS INDEX (PELLETS)

-4

0

4

8

12

1 2 3 4 5

Without Proc. Stab.

Base stabilization:

0,1% AO 1076 +

0,1% Ca-stearate

0.20% PS 168


EXTRUSION PASSES (30 SEC/PASS RESIDENCE TIME)




Reduced blooming of LLDPE film

LLDPE FILM SAMPLES

(DENSITY = 0.917 G/CM3)

AFTER 1 YEAR STORAGE

AT 23 °C (73 °F)


– Excellent solubility of AddWorks LXR 568 in LLDPE

– High transparency / No blooming

– Nonyl-Phenol free solution

– Especially suitable for LLDPE cast film, where a more enhanced stabilisation is needed

Additive formulation:

200 ppm AO +

Processing Stabilizer

PS 168 AddWorks® LXR 568

Strong exudation / “blooming”

Long Term Heat Stabilization


Oven ageing at 150°C Surface Appearance of PP plates according PS class


BS: PP + 0.1% AO 1010 + 0.1% PS + 0.2% Hostanox SE 4 (DSTDP) + 20% Talc

Initial

600

hours

PS 168 PS 626 PS 9228AddWorks

LXR 568No PS

AddWorks LXR 568 allows better surface protection than other processing stabilizers

720

hoursSamples were broken before 720 hours


Color retention of PP plates before and after oven ageing at 150°C


0

20

40

60

80

100

120

140

No PS PS 168 LXR 568 PS 626 PS 9228

YI

Formulations

YI of PP plates before and after oven ageing at 150°C

Initial

600 hours

Formulation: PP + 0.1% PS + 0.1% AO 1010 + 0.2% Hostanox SE 4 + 20% Talc

AddWorks LXR 568 shows less yellowing compared to other processing stabilizers


Mechanical properties retention at 150°C


0

5

10

15

20

25

30

35

40

45

50

No PS PS 168 LXR 568 PS 626 PS 9228

Str

eng

th (M

Pa)

Formulations

Strength at break of PP plates before and after oven ageing at 150°C

0

480 hours

600 hours

Formulation: PP + 0.1% PS + 0.1% AO 1010 + 0.2% Hostanox SE 4 + 20% Talc

Sam

ple

was b

roken

befo

re

600 h

ou

rs

Only AddWorks LXR 568 shows more than 50 % retention of strength at break after 600 hours


Conclusion

– AddWorks LXR 568 shows superior performance on color stability and mechanical

properties retention in PP compound vs most common processing stabilizers in long

term heat stabilization of talc filled PP compounds.

– LXR 568 shows better appearance than PS 168, PS 626 and PS 9228 after oven

ageing at 150°C reaching 600 hr.


Product Form


Product Form

ADDWORKS LXR 568 MP


AddWorks LXR 568 is available as free flow, dust-free micro pills. It is easy to handle.

Key Benefits


AddWorks LXR 568

– shows an outstanding colour stability and excellent MFR stability

– contributes to a superior oven ageing stability

– is easy to handle and is available as free flow, dust-free micro pills.

– shows a retarded formation of NIAS = non intentionally added substances

– does not hydrolyse upon exposure to moisture in the environment. It stays stable if

packaging is accidentally left open or material is transported in hopper cars

– does not hydrolyse and cause black specks as do other phosphites and

phosphonites

– can be fed better under humid conditions. It remains free flowing and full active,

whilst other phosphites or phosphonites turn sticky and lose effectiveness.


high performance stabilizer with enhanced hydrolytic

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